Method of producing a resin acid lactone



Patented Dec. 17, 1940 a UNITED STATES PATENTOFFICE METHOD OF PRODUCING A RESIN ACID 1 LACTONE Torsten Hasselstrom, Savannah, Ga;, assignor to G & A Laboratories, Inc., Savannah, Ga., a corporation of Georgia No Drawing. Application February 28, 1939,

- Serial No. 258,955

7 Claims. (Cl. 260-97) This invention relates to a. method of producproducts so formed. Said treatment comprises ing a resin acid lactone from rosin acids containcontacting the abietyl compound'with acatalyst. ing dihydroabietic acid. hereinafterdeiined, in a manner adapted to ex- It is the object of this invention to provide a clude the possibility of reaction between the method of producing a resin acid lactone belong- 'abietyl compound and any other material; As ing to the tetrahydroresin acid series of hydroa result of such treatment, a change in the chem genated rosin derivatives. ical and physical properties of the abietyl com- The preparation of a resin acid lactone in acpound, believed to be due to a simultaneous decordance with this invention is carried out by hydrogenation and hydrogenation by'the heating l0 treating a rosin acid containing dihydroabietic of the abiety comp in the presence of the 10 acid as one of-its constituents with sulfuric acid hydrogenation catalyst only, takes place and the unoler the usual conditions of sulfonating such resulting product has a greatly decreased. apparrosin acids to. produce the sulfonate. The rosin ent color.

. acids containing dihydroabletic acid useful in .The catalysts which may be used in effecting this invention also contain dehydroabietic acid this intraor intermolecular rearrangement are 15 to a greater or less extent. By treatment'of the those which cata y y o at o of unsaturosinacid with sulfuricacid under the usual'conrated compoundse. g., any of the nickel, platditions of sulfonation, the dehydroabietic acid inum, palladium or copper chromite'catalysts content of the particular rosin acid undergoes us i s h hydrogenation- The H X" r in 2o sulfonation with the formation of the dehydrois kn wn to nta n appreciable qu t s fd abietic acid sulfonate. The dihydroabietic acid y oa acid and dihydroabietic acid- T content of the particular rosin acid, on the other hy ro en ted wood rosin may be the p duct of hand, undergoes hydration by the action of the r sin h d o n a d wi preferably e satu sulfuric acid with theformationof thelactone te to the extent of 50 to, '75 per cent of the,

of hydroxytetrahydroabietic acid. double bonds of the original rosin.

The rosin acids containing dihydroabietic acid The od of producing the resin acid lactone which have been found useful in the process of in accordance with this invention involves the this invention are for example, heat treated wood treatment of the rosin a d Containing ihyd orosin, pseudopimaric acid, Hyex wood rosin, abieticacid with concentrated sulfuric acid, for

hydrogenated wood rosin, etc. examp e. f specific gravity at a temp 30 The heat treated rosin may be the so-called ture in the range of ab t ,5"C. to about +5o pyroabietic acid known to contain a mixture of C. to eifect hydration of the dihydroabietic acid deliydroabietic acid nd hydrogenated bi ti contained in the rosin acid to a resin acid lactone acids, some or the latter being in the form of dif th te ydr d series f y nas hydroabietic acid, or it may be any other heat a d rosin d rivative e .d hyd oabietic acid treated rosin containing dihydroabietic acid as con d i t e rosin a undergoes u f ation one of its constituents. The pseudopimaric acid t a dehydreebietie acid Sulfehate? p 'e useful in the process is hereby defined as the Of the resin acid-lactone from .the dehy product prepared in accordance with the process t o d SulfOhete Other slllfeneted 40 disclosed in United st t tt p t t terial is effected by treatment of the reaction 40 2,072,628, and known to consist essentially of a p ct w t que a i, w ch sap nifies the mixture of dehydroabietic acid and dihydrosulfonated material but does not affect the resin abietic acid. The Hyex rosin useful in the acid lac ne process is hereby defined as the rosin acid pre- In a y ut t p ss in a cordance with pared in accordance with the process disclosed this invention the product obtained by treatment 45 in application for United States Letters Patent, 0f the resin acid Containing d y ab ac d Serial No. 6,403, filed February 13, 1935, refiled with concentrated sulfuric acid is poured onto June 12, 1936, Serial No. 84,877, for Process for cracked ice, the brownish precipitate filtered out, the treatment of abietyl compounds and products washed with cold water, extracted by hot water, produced thereby, now U. S. Patent No. 2,154,629, leaving a brownish, insoluble, semi-solid resin.

which disclose treatment of compounds contain- This resin is subjected to an aqueous alkali treating the hydrocarbon nucleus of abietic acid so as ment, for example, by treatment with alkali hyto decrease their apparent unsaturated character droxides, such as, for example, the hydroxides and possibly increase their melting points and of sodium, potassium, ammonium, caseium, ruimprove their color, and also" discloses treated bidium, etc. The alkalitreatment iscarried out and 250 parts birw of, and the solvent evaporatedrw'I'l'ie resultin product, on standing and cooling, becomesjsoli in part. The solid portion is removed hymn-a tion, and purified by recrystallization; e. g., from a'benzene or toluene solution thereof. -The re- M crystallized resin acid lactone is a. water-white solid having a melting-point [of about, 130; to

132 C. and having,

tion of the solid'fromtheliq "dportiongandrecrystallization fromasuitablelsolvent. i

*Asexamples of the carrying out of the process, ofthis invention the following are illustrative: i

- Example 1 y parts. bycweight of partially refined pseudopimaricacid,meltingpoint 167-469? C;

cracked ice. The brownish precipitate tered out, washed: with coldiwaterfuiit washings clouded when mixed with the sigma liquor,"and the washed precipitate then extrac brownish,

ed three times 1' with boiling water,1leaving'1 a I resin; ,The brownish, insoluble semi-solid resin amountedto {30]- parts: by weight. Then:l000 ,grarns otthev ,brownishinsoluble resin were dissolved'in ,5 liters 013% aqueous sodiurn hydroxide solutiomand the zclouded; brownish, solution heated :under a insoluble semi-solid reflux, condenser for 3 hours, allowed to co and, after standing, the supernatant liqul canted, and an equal volume of water added mixture boiled, allowed to stand ,overnigh much oi the causticainsoluble materiales I be removed by repeated dilution and dec'antation was so removed, and the remainder oi", the caus tic-insoluble material was boiled with," super cellff'extracted withffbenzeneor toIuene; and i this extract usedt'o dissolvetthe,i'nsolublef residue, the benzene or toluene evaporated, leaving a :brownish paste; which, on standing," partly solidified andseparated crystals having approximately the following composition: C 80.58% H 10.25%, and a melting point of 131-132 Cr,

invacuo, as follows: I ratze 1,

, Boiling l Fraction I K point,

, showing evidence ofslig the approximate formula resin acid lactone rnay be purified, ifde sired, by tractionaldistillation in vacuo, separaeightoi sulfuric? acid, specific gravityLBLWere'mixed at about 5: to +5?;1C.,"

stirred for about ZOnnnutes, then poured onto;

to,stand over night.

s and an elti by weight of sulfur were mixed at;about ,5 to +5 C,.,tstirred Xor about 20 minutes then; pouredjonto orackedice;

; the, brownish, precipitate was flltered'outgwashed a, with old water until the washings clouded when rnixedslwith the original liquor and the washed {precipitate extracted 3 times, with boiling water,

leavinga u brownish insoluble f1 semi-solid resin,

, amounting to .40 parts; by weight. ,Thenj1000 Then 180 g Of the abovaepiaste m distmd ramsof the brownish insoluble semi-,solidresln with benzen V to dissolve theinsoluble residue, the benzene or toluene evaporated r leaving a, brownish paste,

tion 5 Waste browno The residue-was a brown, brittle resin On U standing." ,iractions -2-4, inclusive, solidified almost completeiym p suitable solventjie. e. such as, for example," acetone. lbenzerie,alcohol,I

; Small amounts, of l ecomposition. Fraceta, were added totraotions 2-4,,incluslve, and, the, solidportionf, removediroin the liquid part i by filtration, giving absolid melting at about "130, C(andcontaining C 79.9%, H 10.5%, show-l0 the resin acid lactone Efratz ple "Tartsbyiwelgnt or ined byl the, treatment, of ,1 wood rosingaccordingeto the procedure described, in the United mStats Patentappiication, ,filed June 12, 1936, Serial No. 84,877, n0w U; SJPatentNo. 2,154,629,

and 250 parts by weightmi. sulfuric acid, specific stirred for about 20, minutes, then poured fonto cracked ice. The brownish precipitate was mtered bout, washedNwith cold water juntilfthe washings clouded when mixed with :the oriairial,

liquor and -the washed precipitate then extracted three times ,with jboiling water, leaving mbrownish, insoluble semi-solid: resin wlhenlOOOgrarns of, the brownish; cisoluble semi-solid :resin -were dissolved, in 5,1iters, o! 3% aqueous sodium hydroxide solution,: an the, cioudedpbrownish so lution 1 heated l und hours, allowed 150?;

reflux-condenser for ,3

and, after standing, the 1 supernatantlliquid decanted and ,an ,equal vole,

urneiof water added the niixture boiled, allowed lwmuch "of 1 the] caustic insoluble material as could a be: removed:

peated, dilution and: -decantation 1 was, so 5 moved, and the remainder of the caustic-in ble ematerial was, boiled tracted, with *benzene'or 1 t 10.25%, 130 n I,

parts by H a i i Q d 1 rosin saturatedto he extent o1' ;,65% oqbothw double'bondso the;

acid, specific gravity 1.84,

aving approximately,

were dissolved in 5liters of 3% aqueous, sodium supernatantliquld decanted and amequalwvoh eustic-insoluble, ma-

toluene, and this 1 extract used Supercelli'; extracted hydroxide :solution, and the clouded? brownish solution heated under a, reflux condenser for 3 ihoursgallowed to coolgand; afterstanding, ithe, Percent il )umeofwater added, the mixture boiled, allowed to standover night. As much of, theycaustic ainsoluble. materiai 'iasdcould bestremovedby re I ,peated dilution, and decantation awasso removed,

which, on standing, partly solidified and separated crystals havingapproximately the fol-- lowing composition: C 80.58%, H 10.25%, and a melting point of 131-132 C.

While in the above examples, the use of a 3% aqueous solution of sodium hydroxide is specifically disclosed for dissolving the sulfonated pseu- .dopimaric acid, "Hyex rosin or hydrogenated rosin, it will be appreciated that I may use a wide range of concentrations of sodium hydroxide or of other alkaline materials, such as, for example,

potassium hydroxide, sodium carbonate, potassium carbonate, etc., and that my invention is not limited to the use of a 3% aqueous solution of sodium hydroxide. 7

It will also be appreciated that the "Supercell which I use in these examples functions as an aid to the filtration on extraction, and may be recovered and re-used after the removal of the neutral constituents by extraction or otherwise. It will also be appreciated that I may use other filter aids equivalent to Supercell" for this purpose.

It will be understood that the lactone obtained in Examples 2 and 3 above are presumably the same lactone obtained and described in Example 1. It will also be appreciated that the method of purification by fractional distillation may likewise be applied to the lactone produced in Examples 2 and 3.

In proceeding in accordance with this invention, I may also obtain a valuable resin from the alkaline solution which I separate from the neutral fraction containing my new lactone. I accomplish this by treating the alkaline solution with a suitable acid to neutralize the alkali, whereupon the resinous material precipitates from its solution. This resinous material, after separation from the solution, washing free of alkali and being fused, has the very high melting point of 110 C. It also has the particularly valuable property oi stability against crystallization from solutions of its solvents, such as, for example, alcohol, hydrocarbons, ketones, esters, etc.

My resin acid lactone is variously useful in the preparation of varnishes and as a plasticizer where hydrogenated derivatives of resin acids are useful, as a raw material for the preparation of hydroxy acids, adhesives, etc.

The product in accordance with this invention possesses superior properties as to stability toward atmospheric conditions, as compared to natural rosin, is economical to prepare, as compared to hydrogenated rosin derivatives, and requires no complicated isolation, being obtainable by a very simple process of extraction and distillation,

The clear, alkali solutions obtained in my process of digestion of the brownish, insoluble residue from sulfonation, are useful as an emulsifying agent for rosin, hydrogenated rosin, rosin size, and other purposes where a stable emulsiflcation is required.

It will be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited'thereby.

This application is a continuation-in-part of my application for United States Patent, .Serial No. 208,854, filed May 19, 1938 on "Resin acid lactone and method of producing".

What I claim and desire to protect by Letters Patent is:

1. Process of producing a resin acid lactone which includes sulfonatlng a rosin. acid which contains dihydroabietic acid and dehydroabietic acid as constituents by treatment with concentrated sulfuric acid at a temperature within the range of about -5 C. to about 50" C. under conditions which promote sulfonation, treating the resultant product to remove sulfonation products and other water-soluble bodies therefrom, and

leave an insoluble residue, treating said insoluble residue with aqueous caustic alkali, and recovering a crude resin acid lactone from the caustic insoluble residue.

2. Process of producing a resin acid lactone which includes sulfonating a rosin acid which contains dihydroabietic acid and dehydroabietic acid as constituents by treatment with concentrated sulfuric acid at a temperature within the range of about 5 C. to about 50 C. under conditions which promote sulfonation, treating the resultant product to remove sulfonation products 4. Process as in claim 2 wherein the rosin acid is pseudopimaric acid.

5. Process as in claim 2 wherein the rosin acid is Hyex wood rosin.

6. Process as in claim 2 wherein the rosin acid is hydrogenated wood rosin containing dihydroabietic acid and dehydroabietic acid as constituents.

7. The process as in claim 2 wherein the rosin acid is a hydrogenated rosin containing dihydroabietic acid and dehydroabietic acid.

TORSTEN HASSELSTROM. 

